CN106800552A - A kind of 3,3 ' join carbazole analog derivative electroluminescent organic material and its application - Google Patents

A kind of 3,3 ' join carbazole analog derivative electroluminescent organic material and its application Download PDF

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CN106800552A
CN106800552A CN201611114044.2A CN201611114044A CN106800552A CN 106800552 A CN106800552 A CN 106800552A CN 201611114044 A CN201611114044 A CN 201611114044A CN 106800552 A CN106800552 A CN 106800552A
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electroluminescent organic
analog derivative
compound
organic material
base
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CN106800552B (en
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柳佳欣
陈慕欣
王剑平
胡晓腾
储毅
孙海洋
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Yantai Jiumu Chemical Co., Ltd
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JIUMU CHEMICAL PRODUCT CO Ltd YANTAI
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Abstract

The invention discloses 3,3' of one kind connection carbazole analog derivative electroluminescent organic material and its application, above-mentioned 3,3' connection carbazole analog derivative electroluminescent organic material has molecular structure as follows：Wherein, R1Selected from the one kind in phenyl, xenyl, terphenyl, naphthyl, fluorenyl, benzofuranyl, benzothienyl, dibenzofuran group, dibenzothiophenes base, pyrenyl, phenanthryl, benzfluorene ketone group.3 provided in the present invention, 3' joins carbazole analog derivative electroluminescent organic material electroluminescent organic material, it is applied in OLED luminescent devices, the external quantum efficiency of device, power efficiency and current efficiency are all highly improved, and the service life of device also has obvious extension, with good market prospects.

Description

A kind of 3,3 ' join carbazole analog derivative electroluminescent organic material and its application
Technical field
The present invention relates to field of organic electroluminescent materials, more particularly to 3,3' of one kind connection carbazole analog derivative organic electroluminescences Luminescent material and its application.
Background technology
Organic electroluminescent diode (OLED) results from the eighties in last century, with self-luminous, wide viewing angle, response speed Many advantages, such as hurry up, be capable of achieving Flexible Displays, this becomes the most favourable competitor of flat panel display of future generation, by people Greatly concern, and by the development of more than two decades, the technology progressively moves to maturity.
At present, organic electroluminescent technology, is mainly used in two fields, and respectively full-color display and white light shine It is bright, based on the commodity of OLED Display Techniques, industrialization is done step-by-step, such as, in commodity such as smart mobile phone, curved surface TVs In, this technology is applied widely.
Material for organic electroluminescence device mainly includes electrode material, carrier transmission material, luminescent material, its Middle luminescent material occupies critical positions in OLED.
In order to realize full-color display, three kinds of luminescent devices of color of red, green, blue are respectively necessary for, with red device and green glow Device is compared, and blue luminescent device is still not mature enough, and device lifetime and efficiency are relatively low.People pass through ultra clean technology and encapsulation skill Art, exploitation has blue light material of high glass-transition temperature etc. to improve the life-span of blue-light device, and doping techniques and exploitation New material with the two poles of the earth structure, then be the direction for improving device efficiency.
Doping techniques are reduced by the way that luminescent material (guest materials) is dispersed among other materials (material of main part) The concentration of luminescent material, so as to avoid intermolecular aggregation and concentration quenching, and then realizes improving device efficiency, improves electroluminescent Excitation, extends the purpose of device lifetime.
For the actual demand of current OLED display Lighting Industries, the development of current OLED material is also far from enough, falls After the requirement of panel manufacturing enterprise, it is particularly important as the organic functional material of material enterprise development higher performance.
The content of the invention
For the above mentioned problem that existing OLED material is present, now providing a kind of new 3,3' connection carbazole analog derivatives has Electroluminescent material and its application, such material can be applied in organic electroluminescence device as luminescent material so that Such organic electroluminescence device has power efficiency and current efficiency higher.
Concrete technical scheme is as follows：
The first aspect of the invention is to provide 3,3' of one kind connection carbazole analog derivative electroluminescent organic materials, with this The feature of sample, electroluminescent organic material has the molecular structure shown in formula (I)：
In formula (I), R1Selected from containing substituted base or without the substitution xenyl of base, terphenyl, naphthyl, anthryl, fluorenyl, One kind in pyrenyl or phenanthryl, preferably
In one kind；R2And R3Separately it is selected from and contains Substituted base or without substitution base benzofuranyl, benzothienyl, benzfluorene ketone group, Fluorenone base, dibenzofuran group, hexichol One kind in bithiophene base or triazine radical, it is preferred that R2、R3Separately it is selected from In one kind.
Preferably, 3, the 3' connection carbazole analog derivative electroluminescent organic materials for being provided in the present invention are following 1-95 structures Any one in formula：
The second aspect of the invention is to provide a kind of 3,3' connection carbazole analog derivative electroluminescent organic materials and is preparing Application in organic electroluminescence device.
The third aspect of the invention is to provide a kind of organic electroluminescence device, contains in the organic electroluminescence device Multiple functional layers, also have the feature that, at least one functional layer contains above-mentioned 3,3' connection carbazole analog derivative Organic Electricity Electroluminescent material.
Prepared electroluminescent organic material generally comprises transparent substrate layer, the transparency electrode being sequentially overlapped in the present invention Layer, hole injection layer, hole transmission layer, luminescent layer (are related to the having with 3,3' connection carbazole analog derivatives provided in the present invention Electroluminescent material), electron transfer layer, electron injecting layer (LiF) and negative electrode reflection motor layer (Al), all functional layers adopt It is made of vacuum evaporation process.
It should be appreciated that making the purpose of OLED in the present invention, it is intended merely to be better described, is provided in the present invention The electroluminescent ability that 3,3' connection carbazole analog derivative electroluminescent organic materials have, and be not to provided by the present invention Electroluminescent organic material range of application limitation.
The beneficial effect of such scheme is：
3, the 3' connection carbazole analog derivative electroluminescent organic materials provided in the present invention, are applied to OLED luminescent devices In, the external quantum efficiency of device, power efficiency and current efficiency are all highly improved, and the service life of device also has Obvious extension, with good market prospects.
Brief description of the drawings
Fig. 1 is the structural representation of the organic electroluminescence device of offer in embodiments of the invention, by lower floor to upper strata, It is followed successively by transparent substrate layer (1), transparent electrode layer (2), hole injection layer (3), hole transmission layer (4), luminescent layer (5), electronics Transport layer (6), electron injecting layer (7), negative electrode reflection electrode layer (8), wherein, luminescent layer (5) is related to provided in the present invention 3,3' connection carbazole analog derivative electroluminescent organic material.
Specific embodiment
The technical scheme in the embodiment of the present invention is clearly and completely described below in conjunction with the embodiment of the present invention, Obviously, described embodiment is only a part of embodiment of the invention, rather than whole embodiments.Based in the present invention Embodiment, the every other embodiment that those of ordinary skill in the art are obtained on the premise of creative work is not made, Belong to the scope of protection of the invention.
It should be noted that in the case where not conflicting, the embodiment in the present invention and the feature in embodiment can phases Mutually combination.
The preparation of the compound 1 of embodiment 1
The synthetic route of compound 1 is：
Wherein, the preparation method of compound C is：Under the protection of nitrogen, to the there-necked flask of 500ml, 33.2g chemical combination is added Thing A (100mmol), 20.9g compounds B (90mmol), 3.8g cuprous iodides (20mmol), 42.4g tripotassium phosphates (200mmol), 200g dimethylbenzene, is heated to reflux 24 hours, and TLC is tracked to without compound B.Reaction is finished, and is cooled to 30 DEG C, mistake Filter, dimethylbenzene 50ml*3 drip washing, filtrate washing 200g*3 to pH=7, after organic phase is dried, normal pressure crosses silicagel column.Cross post to finish, two Toluene 50ml*2 drip washing pillars, drip washing is finished, and leacheate is merged into decompression abjection solvent with post liquid is crossed, and desolventizing is complete to add 300ml Ethanol is recrystallized twice with 50ml toluene mixed solutions, and 34.9g compound C, yield are obtained after drying：80%, HPLC：98.8%.
HPLC-MS：Compound C theoretical moleculars are 485, and actually detected result molecular weight is 485.1.
The preparation method of compound F is：Under the protection of nitrogen, to the there-necked flask of 500ml, 41.7g compounds D is added (100mmol), 14.8g compounds E (90mmol), 0.04g palladiums (0.2mmol), 21.2g sodium carbonate (200mmol), 200g Toluene, is heated to reflux 12 hours, and TLC is tracked to without compound E.Reaction is finished, and is cooled to 30 DEG C, is filtered, toluene 50ml*3 drip washing, Filtrate washes 200g*3 to pH=7, and after organic phase is dried, normal pressure crosses silicagel column.Cross post to finish, toluene 50ml*2 drip washing silicagel columns, Drip washing is finished, and leacheate is merged into decompression abjection solvent with post liquid is crossed, and desolventizing is complete to add 300ml ethanol to mix molten with 50ml toluene Liquid is recrystallized twice, and 27.7g compound F, yield are obtained after drying：75%, HPLC：99.5%.
HPLC-MS：Compound F theoretical moleculars are 408, and actually detected result molecular weight is 408.5.
The preparation method of compound H is：Under the protection of nitrogen, to the there-necked flask of 500ml, 40.8g compounds F is added (100mmol), 16.2g compounds G (90mmol), 0.04g palladiums (0.2mmol), 21.2g sodium carbonate (200mmol), 200g Toluene, is heated to reflux 12 hours, and TLC is tracked to without compound G.Reaction is finished, and is cooled to 30 DEG C, is filtered, toluene 50ml*3 drip washing, Filtrate washes 200g*3 to pH=7, and after organic phase is dried, normal pressure crosses silicagel column.Cross post to finish, toluene 50ml*2 drip washing silicagel columns, Drip washing is finished, and leacheate is merged into decompression abjection solvent with post liquid is crossed, and desolventizing is complete to add 300ml ethanol to mix molten with 50ml toluene Liquid is recrystallized twice, and 32.6g compound H, yield are obtained after drying：78%, HPLC：99.5%.
HPLC-MS：Compound H theoretical moleculars are 464, and actually detected result molecular weight is 464.2.
The preparation method of compound 1 is：Under the protection of nitrogen, to the there-necked flask of 500ml, 40.8g compounds C is added (100mmol), 16.2g compounds H (95mmol), the triphenylphosphines of 0.04g tetra- close palladium (10mmol), 21.2g sodium tert-butoxides (150mmol), 200g dimethylbenzene, is heated to reflux 24 hours, and TLC is tracked to without compound H.Reaction is finished, and is cooled to 30 DEG C, mistake Filter, dimethylbenzene 50ml*3 drip washing, filtrate washing 200g*3 to pH=7, after organic phase is dried, normal pressure crosses silicagel column.Cross post to finish, two Toluene 50ml*2 drip washing silicagel columns, drip washing is finished, and leacheate is merged into decompression abjection solvent with post liquid is crossed, and desolventizing is complete to be added 300ml ethanol is recrystallized twice with 50ml toluene mixed solutions, and 69.4g compounds 1, yield are obtained after drying：80%, HPLC： 99.8%.
HPLC-MS：The theoretical molecular of compound 1 is 913, and actually detected result molecular weight is 913.4.
The preparation of the compound 2 of embodiment 2
The synthetic route of compound 2 is：
Wherein, the preparation method of compound J is：Under the protection of nitrogen, to the there-necked flask of 500ml, 33.2g chemical combination is added Thing A (100mmol), 27.7g compounds I (90mmol), 3.8g cuprous iodides (20mmol), 42.4g tripotassium phosphates (200mmol), 200g dimethylbenzene, is heated to reflux 24 hours, and TLC is tracked to without compound I.Reaction is finished, and is cooled to 30 DEG C, mistake Filter, dimethylbenzene 50ml*3 drip washing, filtrate washing 200g*3 to pH=7, after organic phase is dried, normal pressure crosses silicagel column.Cross post to finish, two Toluene 50ml*2 drip washing silicagel columns, drip washing is finished, and leacheate is merged into decompression abjection solvent with post liquid is crossed, and desolventizing is complete to be added 300ml ethanol is recrystallized twice with 50ml toluene mixed solutions, and 42.9g compound J, yield are obtained after drying：85%, HPLC： 99.0%.
HPLC-MS：Compound J theoretical moleculars are 561, and actually detected result molecular weight is 561.3.
The preparation method of compound 2 is：Under the protection of nitrogen, to the there-necked flask of 500ml, 40.8g compounds J is added (100mmol), 16.2g compounds H (95mmol), the triphenylphosphines of 0.04g tetra- close palladium (10mmol), 21.2g sodium tert-butoxides (150mmol), 200g dimethylbenzene, is heated to reflux 24 hours, and TLC is tracked to without compound H.Reaction is finished, and is cooled to 30 DEG C, mistake Filter, dimethylbenzene 50ml*3 drip washing, filtrate washing 200g*3 to pH=7, after organic phase is dried, normal pressure crosses silicagel column.Cross post to finish, two Toluene 50ml*2 drip washing silicagel columns, drip washing is finished, and leacheate is merged into decompression abjection solvent with post liquid is crossed, and desolventizing is complete to be added 300ml ethanol is recrystallized twice with 50ml toluene mixed solutions, and 78.8g compounds 2, yield are obtained after drying：84%, HPLC： 99.8%.
HPLC-MS：The theoretical molecular of compound 2 is 988, and actually detected result molecular weight is 988.2.
The preparation of the compound 3 of embodiment 3
The synthetic route of compound 3 is：
Wherein, the preparation method of compound K is：Under the protection of nitrogen, to the there-necked flask of 500ml, 33.2g chemical combination is added Thing A (100mmol), 18.5g compounds J (90mmol), 3.8g cuprous iodides (20mmol), 42.4g tripotassium phosphates (200mmol), 200g dimethylbenzene, is heated to reflux 24 hours, and TLC is tracked to without compound J.Reaction is finished, and is cooled to 30 DEG C, mistake Filter, dimethylbenzene 50ml*3 drip washing, filtrate washing 200g*3 to pH=7, after organic phase is dried, normal pressure crosses silicagel column.Cross post to finish, two Toluene 50ml*2 drip washing silicagel columns, drip washing is finished, and leacheate is merged into decompression abjection solvent with post liquid is crossed, and desolventizing is complete to be added 300ml methyl alcohol is recrystallized twice with 50ml toluene mixed solutions, and 30.5g compound Ks, yield are obtained after drying：74%, HPLC： 98.5%.
HPLC-MS：Compound K theoretical molecular is 458, and actually detected result molecular weight is 458.2.
The preparation method of compound 3 is：Under the protection of nitrogen, to the there-necked flask of 500ml, 45.8g compound Ks are added (100mmol), 16.2g compounds H (95mmol), the triphenylphosphines of 0.04g tetra- close palladium (10mmol), 21.2g sodium tert-butoxides (150mmol), 200g dimethylbenzene, is heated to reflux 48 hours, and TLC is tracked to without compound H.Reaction is finished, and is cooled to 30 DEG C, mistake Filter, dimethylbenzene 50ml*3 drip washing, filtrate washing 200g*3 to pH=7, after organic phase is dried, normal pressure crosses silicagel column.Cross post to finish, two Toluene 50ml*2 drip washing silicagel columns, drip washing is finished, and leacheate is merged into decompression abjection solvent with post liquid is crossed, and desolventizing is complete to be added 300ml methyl alcohol is recrystallized twice with 50ml toluene mixed solutions, and 37.9g compounds 1, yield are obtained after drying：45%, HPLC： 99.8%.
HPLC-MS：The theoretical molecular of compound 3 is 886, and actually detected result molecular weight is 885.7.
The preparation of the compound 4 of embodiment 4
The synthetic route of compound 4 is：
The preparation method of compound M is：Under the protection of nitrogen, to the there-necked flask of 500ml, 33.2g compounds A is added (100mmol), 22.0g compound Ls (90mmol), 3.8g cuprous iodides (20mmol), 42.4g tripotassium phosphates (200mmol), 200g dimethylbenzene, is heated to reflux 24 hours, and TLC is tracked to without compound L.Reaction is finished, and is cooled to 30 DEG C, filtering, dimethylbenzene 50ml*3 drip washing, filtrate washing 200g*3 to pH=7, after organic phase is dried, normal pressure crosses silicagel column.Cross post to finish, dimethylbenzene 50ml* 2 drip washing silicagel columns, drip washing finish, by leacheate with cross post liquid merges decompression abjection solvent, desolventizing finish addition 300ml methyl alcohol and 50ml toluene mixed solutions are recrystallized twice, and 29.0g compound M, yield are obtained after drying：65%, HPLC：97.5%.
HPLC-MS：Compound M theoretical moleculars are 496, and actually detected result molecular weight is 496.2.
The preparation method of compound 4 is：Under the protection of nitrogen, to the there-necked flask of 500ml, 49.6g compounds M is added (100mmol), 16.2g compounds H (95mmol), the triphenylphosphines of 0.04g tetra- close palladium (10mmol), 21.2g sodium tert-butoxides (150mmol), 200g dimethylbenzene, is heated to reflux 48 hours, and TLC is tracked to without compound H.Reaction is finished, and is cooled to 30 DEG C, mistake Filter, dimethylbenzene 50ml*3 drip washing, filtrate washing 200g*3 to pH=7, after organic phase is dried, normal pressure crosses silicagel column.Cross post to finish, two Toluene 50ml*2 drip washing silicagel columns, drip washing is finished, and leacheate is merged into decompression abjection solvent with post liquid is crossed, and desolventizing is complete to be added 300ml methyl alcohol is recrystallized twice with 50ml toluene mixed solutions, and 48.3g compounds 4, yield are obtained after drying：55%, HPLC： 99.3%.
HPLC-MS：The theoretical molecular of compound 4 is 924, and actually detected result molecular weight is 924.7.
The preparation of the compound 5 of embodiment 5
The synthetic route of compound 5 is：
The preparation method of compound O is：Under the protection of nitrogen, to the there-necked flask of 500ml, 36.8g compound Ns are added (100mmol), 32.8g compounds E (200mmol), 0.04g palladiums (0.2mmol), 21.2g sodium carbonate (200mmol), 200g toluene, is heated to reflux 24 hours, and TLC is tracked to without compound N.Reaction is finished, and is cooled to 30 DEG C, filtering, toluene 50ml*3 Drip washing, filtrate washing 200g*3 to pH=7, after organic phase is dried, normal pressure crosses silicagel column.Cross post to finish, toluene 50ml*2 drip washing silicon Glue post, drip washing is finished, and leacheate is merged into decompression abjection solvent with post liquid is crossed, and desolventizing is complete to add 300ml ethanol and 50ml toluene Mixed solution is recrystallized twice, and 26.0g compound O, yield are obtained after drying：58%, HPLC：98.5%.
HPLC-MS：Compound O theoretical moleculars are 448, and actually detected result molecular weight is 448.6.
The preparation method of compound 5 is：Under the protection of nitrogen, to the there-necked flask of 500ml, 49.6g compounds M is added (100mmol), 42.6g compounds O (95mmol), the triphenylphosphines of 0.04g tetra- close palladium (10mmol), 21.2g sodium tert-butoxides (150mmol), 200g dimethylbenzene, is heated to reflux 48 hours, and TLC is tracked to without compound O.Reaction is finished, and is cooled to 30 DEG C, mistake Filter, dimethylbenzene 50ml*3 drip washing, filtrate washing 200g*3 to pH=7, after organic phase is dried, normal pressure crosses silicagel column.Cross post to finish, two Toluene 50ml*2 drip washing silicagel columns, drip washing is finished, and leacheate is merged into decompression abjection solvent with post liquid is crossed, and desolventizing is complete to be added 300ml methyl alcohol is recrystallized twice with 50ml toluene mixed solutions, and 53.5g compounds 5, yield are obtained after drying：62%, HPLC： 99.4%.
HPLC-MS：The theoretical molecular of compound 5 is 908, and actually detected result molecular weight is 908.4.
Organic electroluminescence device embodiment
Organic electroluminescence device 1-5 is prepared with compound 1-5 respectively in embodiments of the invention 6-10, wherein, The preparation method of above-mentioned organic electroluminescence device is as follows：
A) photoetching and etching are carried out to the transparent electrode layer (the thickness 215nm of transparent electrode layer) with transparent substrate layer, The figure of the regular transparent electrode layer needed for forming it into, then carries out alkali cleaning, high purity water successively to glass transparent substrate layer Washing, organic phase carries out ultraviolet-ozone washing to remove the organic residue of transparency electrode layer surface again after drying；
B) the vacuum evaporation hole injection layer on transparent electrode layer, thickness is 60nm；
C) on hole injection layer, vacuum evaporation hole transmission layer, thickness is 10nm；
C) on hole transmission layer, vacuum evaporation luminescent layer, thickness is 20nm；
D) on luminescent layer, vacuum evaporation electron transfer layer, thickness is 25nm；
G) on electron transfer layer, vacuum evaporation electron injecting layer (LiF), thickness is 1nm；
F) on electron injecting layer, vacuum evaporation reflection electrode layer (Al), thickness is 130nm.
Meanwhile, comparative device is prepared with the preparation method of above-mentioned organic electroluminescence device in the present invention, wherein, device 1- 5 and comparative device in principal structural layer it is as shown in the table：
In upper table, the structural formula of organic compound A1 is
The structural formula of organic compound B1 is
The structural formula of organic compound C1 is
The structural formula of organic compound D1 is
The above-mentioned device 1-5 for preparing is coupled together anode and negative electrode with drive circuit after completing, and profit With the luminous efficiency of briliancy analyzer (Co., Ltd.'s TOPCON systems, trade name BM7) measurement device, luminescent spectrum and device I-E characteristic, the performance of each device is as shown in the table：
Drawn by upper table analysis, the photophore prepared as OLED luminescent materials using electroluminescent organic material of the present invention Part, the OLED luminescent devices of relatively existing application, is respectively provided with greater advantage, with good in luminous efficiency and excitation aspect of performance Industrialization prospect.
Preferred embodiments of the present invention are these are only, embodiments of the present invention and protection domain is not thereby limited, it is right For those skilled in the art, should can appreciate that all utilization description of the invention and equivalent done by diagramatic content are replaced Change and obviously change resulting scheme, should be included in protection scope of the present invention.

Claims (6)

1. one kind 3,3' connection carbazole analog derivative electroluminescent organic materials, it is characterised in that the electroluminescent organic material It is the small molecule of the structure centered on 3,3' connection carbazoles, shown in its molecular structure such as formula (I)：
In formula (I), R1Selected from containing substituted base or without substitution base xenyl, terphenyl, naphthyl, anthryl, fluorenyl, pyrenyl or One kind in phenanthryl, R2And R3Separately selected from benzofuranyl, the benzothiophene containing substituted base or without substitution base One kind in base, benzfluorene ketone group, Fluorenone base, dibenzofuran group, dibenzothiophenes base or triazine radical.
2. 3,3' according to claim 1 joins carbazole analog derivative electroluminescent organic material, it is characterised in that the R1 Selected from the one kind in xenyl, terphenyl, naphthyl, anthryl, fluorenyl, pyrenyl or phenanthryl.
3. 3,3' according to claim 2 joins carbazole analog derivative electroluminescent organic material, it is characterised in that the R2 Selected from benzofuranyl, benzothienyl, benzfluorene ketone group, Fluorenone base, dibenzofuran group, dibenzothiophenes base or triazine radical In one kind.
4. 3,3' according to claim 2 joins carbazole analog derivative electroluminescent organic material, it is characterised in that the R3 Selected from benzofuranyl, benzothienyl, benzfluorene ketone group, Fluorenone base, dibenzofuran group, dibenzothiophenes base or triazine radical In one kind.
5. prepared by a kind of 3,3' connection carbazole analog derivative electroluminescent organic materials according to claim any one of 1-4 Application in organic electroluminescence device.
6. a kind of organic electroluminescence device, including multiple functional layers, it is characterised in that at least one described functional layer contains 3,3' connection carbazole analog derivative electroluminescent organic materials described in claim any one of 1-4.
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WO2015178732A1 (en) * 2014-05-23 2015-11-26 Rohm And Haas Electronic Materials Korea Ltd. Multi-component host material and an organic electroluminescence device comprising the same
CN105441067A (en) * 2015-11-23 2016-03-30 中节能万润股份有限公司 Organic electroluminescent material as well as preparation method and application thereof

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KR20150012835A (en) * 2013-07-26 2015-02-04 덕산하이메탈(주) An organic electronic element comprising a layer for improving light efficiency, and an electronic device comprising the same
US20150179949A1 (en) * 2013-12-20 2015-06-25 Samsung Display Co., Ltd. Material for organic electroluminescence device and organic electroluminescence device using the same
WO2015178732A1 (en) * 2014-05-23 2015-11-26 Rohm And Haas Electronic Materials Korea Ltd. Multi-component host material and an organic electroluminescence device comprising the same
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